Polymer mixtures for printed polymer electronic circuits

ABSTRACT

In order to increase the viscosity of semiconductive polymers in solution, they are mixed with non-semiconductive polymers.

Plastics (polymers) are known as insulators. However, there are also some remarkable polymers having conductive and even semiconductive properties. All three properties taken together permit the production of fully functioning integrated circuits from polymers. The attraction of polymer electronics lies in its simple producability because the polymers can be deposited from the solution to give layers. This means that in particular it is possible to use inexpensive printing techniques by means of which the individual structured layers of integrated circuits can be produced. However, every printing process sets specific requirements with regard to the substances to be printed, in this case the polymer solutions. It is rare that the properties of the polymer solutions comply with the printing requirements from the outset. Thus, for example, the viscosity of the polymer solutions is considerably too low for most printing processes. This applies in particular to polymeric semiconductor material.

An inkjet technique for printing low-viscosity semiconductor material is known from Nalwa H. S. (editor): “Organic Conductive Molecules and Polymers”, volume 2, 1997, pages 334 to 335). Inkjet printing is, however, least favored for mass production.

Starting from this, it is the object of the invention to make semiconductive polymers accessible to standard printing processes.

This object is achieved by the inventions stated in the independent claims. Advantageous developments are evident from the dependent claims.

Accordingly, a polymer mixture, in particular a polymer solution, contains one or more semiconductive polymers and one or more non-semiconductive, i.e. insulating and/or conductive polymers.

Polythiophene, in particular poly(3-hexylthiophene) (P3HT), has proven particularly advantageous as a semiconductive polymer. However, the use of polyfluorene or polythienylenevinylene and a mixture of two or three of said semiconductive polymers is also possible.

Polystyrene (PS), polymethyl methacrylate (PMMA), cymel and polyisobutyl (PIB) or mixtures thereof have proven particularly suitable as non-semiconductive polymers.

In order to obtain a polymer solution, solvents may also be present in the polymer mixture, in particular chloroform, toluene, ketones, dioxane and/or heptane.

In addition, the polymer mixture may contain conductive polymers, oligomers, conductive molecules and/or semiconductive molecules (monomers, “small molecules”, in particular pentacene and/or C60), particles and other materials which cannot be dissolved, or may consist of a selection of said substances and possibly customary additives.

By said mixing of semiconductive and non-semiconductive polymers, it is possible to establish the desired viscosity of the polymer solution. Preferably, a viscosity of more than 8 mPa·s is established, in particular more than 80 mPa·s. As a result, the polymer solution is suitable for screen printing or pad printing and further standard printing processes.

A polymer mixture of the type described can preferably be used in a printing process, in particular in a screen printing, flexographic printing, offset printing, gravure printing and/or pad printing process.

By means of a polymer mixture of the type described, it is possible to produce a double layer which contains one or more semiconductive polymers in its first layer and one or more non-semiconductive polymers in its second layer.

This can be effected, for example, in a process for the production of the double layer in which a polymer mixture of the type described is used, which polymer mixture separates on deposition from the solution and thus forms the double layer.

A printed electronic circuit can be produced using a polymer mixture of the type described, it being possible to create semiconductive polymer structures by screen printing and/or pad printing during the production. Alternatively or in addition, the polymer mixture can also be used generally for the production of electrical components, for example for organic transistors, diodes, capacitors, resistors, light emitting diodes, photovoltaic cells, photodetectors, display elements, etc.

Preferred developments of the printing process, of the double layer, of the process for the production of the double layer and of the electronic circuit arise from the preferred developments of the polymer mixture, and vice versa.

Further advantages and features of the invention are evident from the description of working examples with reference to the drawing.

FIG. 1 shows the characteristic of an organic field effect transistor having a semiconductive layer which consists purely of semiconductive polymer;

FIG. 2 shows the characteristic of an organic field effect transistor having a semiconductive layer which consists of non-semiconductive polymer and semiconductive polymer in the weight ratio 1:3;

FIG. 3 shows the characteristic of an organic field effect transistor having a semiconductive layer which consists of non-semiconductive and semiconductive polymer in the weight ratio 1:1.

It is proposed to mix the functional, i.e. semiconductive polymers with other polymers in order in this manner to achieve an adaptation to a wide range of printing requirements. The mixing of polymers (polymer blends) is a customary method for obtaining certain combinations of properties. However, in the case of the semiconductor polymers, such mixtures have not yet been considered. If such a mixture were to be considered theoretically, virtually complete disappearance of the semiconductive properties would be expected for semiconductor polymers as a result of addition of other materials. However, our own experiments show that this is not the case.

Polythiophene, as a semiconductive polymer, was mixed with polystyrene and polymethyl methacrylate. It is found that the semiconductor function is retained in the mixed polymer system too. At the same time, the corresponding polymer solution has an increased viscosity, which makes it more readily printable.

The reason why the semiconductive properties are so well retained is not exactly known, but two arguments appear possible. Firstly, polyaniline is a conductive polymer. Like polythiophene, it belongs to the class of the conjugated polymers. In polymer mixtures, it retains its conductive function to a high degree, as described in Speakman S. P. et al.: “Organic Electronics 2 (2)”, 2001, pages 65 to 73. What is true here for polyaniline may apparently also be applied to polythiophene. Secondly, it is a known phenomenon that polymer mixtures tend to separate after deposition from solution. This is described, for example, in Garbassi F. et al.: “Polymer Surfaces”, 1998, pages 289 to 300. The polymer system minimizes its total energy by virtue of the fact that the material having the lower surface energy forms the uppermost layer.

In our case, two layers form, the first of which substantially comprises the admixed polymer (PS or PMMA). The second layer is a virtually pure polythiophene layer. It imparts the semiconductor property to the system. What has been demonstrated here for polythiophene by way of example is also possible with other semiconductive polymers, for example polyfluorene and polythienylenevinylene.

FIGS. 1 to 3 show the characteristics of three organic field effect transistors (OFETs) having different mass ratios of polystyrene (PS) and poly(3-hexylthiophene) (P3HT) in the semiconductive layer. In FIG. 1, the ratio of PS to P3HT is 0:100, in FIG. 2 the ratio of PS to P3HT is 25:75 and in FIG. 3 the ratio of PS to P3HT is 50:50. The layer thicknesses are unchanged for better comparison.

The OFETs comprising PS and P3HT, whose, characteristics are shown in FIGS. 2 and 3, function just as well as the OFET comprising P3HT, whose characteristics are shown in FIG. 1, except that the current decreases with increasing proportion of PS. Since, however, the OFF current decreases more sharply than the ON current, the transistor characteristic of the ON/OFF ratio even improves.

A further tested working example is the system P3HT and polyisobutyl (PIB). At maximum solubility of 2.5% of polymer solid in chloroform, P3HT has a viscosity of 2 mPa·s. By adding PIB dissolved in heptane the viscosity can be increased to values up to 100 mPa·s, depending on the mixing ratio. This meets the requirements of screen printing, in which the viscosity must be greater than or equal to 10 mPa·s, and of pad printing, in which the viscosity must be greater than or equal to 100 mPa·s. In experiments, operable OFETs have also been produced with this semiconductor mixture.

By means of the invention, the properties of different polymers are combined with one another. For example, polythiophene contributes the semiconductive property and polystyrene the higher viscosity in the polymer solution. Polythiophene alone in solution would not be readily printable owing to the excessively low viscosity, whereas the addition of polystyrene imparts higher viscosity to the solution, which makes it more readily printable. Further advantages are to be seen for the case of the abovementioned separation. They relate to the solid double layer, for example of insulator and semiconductor, remaining behind after evaporation of the solvent. Specifically, the advantages are as follows:

-   -   saving of an operation by simultaneous production of the two         layers,     -   production of an extremely thin semiconductor layer, which is         not possible by direct printing of only the semiconductor         solution,     -   perfect bonding (adhesion) of the two layers to one another,     -   the layers rest on one another in exact register, particularly         in printed structures (self-alignment),     -   the solvent compatibility does not play a role, i.e. there is no         partial dissolution of the lower layer on application of the         upper layer,     -   it is to be expected that the special method of layer formation         by separation has a positive influence on the layer quality, for         example with regard to low defect density and high structural         order of the (conjugated) polymers. 

1. A printable polymer mixture for the preparation of a double layer comprising a semiconductor layer and a non-semiconductive layer wherein the mixture exhibits semiconductive properties, the mixture comprising: one or more semiconductive polymers; and one or more non-semiconductive polymers, in a solution comprising a non-electrolytic solvent to form said printable mixture and said double layer.
 2. The polymer mixture as claimed in claim 1 wherein the semiconductive polymers include at least one of the group consisting of polythiophene, polyfluorene or polythienylenevinylene.
 3. The polymer mixture as claimed in claim 1 wherein the non-semiconductive polymers are selected from the group consisting of at least one of polystyrene, polymethyl methacrylate, cymel or poly isobutyl.
 4. The polymer mixture as claimed in claim 1 wherein said solvent includes at least one of chloroform, toluene, ketones, dioxane or heptane.
 5. The polymer mixture as claimed in claim 1 wherein the mixture it additionally contains molecules which are smaller than polymers, in particular oligomers, conductive molecules or semiconductive molecules.
 6. The polymer mixture as claimed in claim 1 wherein the mixture further includes additives.
 7. The polymer mixture as claimed in claim 1 wherein the mixture has a viscosity of more than 8 mpa·s.
 8. A printing process for the production of a semiconductive double layer by a known process, selected from the group consisting of at least one of screen printing, flexographic printing, offset printing, gravure printing and/or pad printing process, the polymer mixture as claimed in claim 1 being used as a print medium in the known process.
 9. A printing process for the production of a semiconductive double layer by a known process, selected from the group consisting of screen printing, flexographic printing, offset printing, gravure printing and/or pad printing process, the double layer produced by printing a printing medium comprising the polymer mixture of claim 1 for forming the one or more semiconductive polymers in a first of its layers, and the one or more non-semiconductive polymers in a second of its layers.
 10. An electronic component which is produced using a polymer mixture as claimed in claim
 1. 11. An electronic component which is produced using a polymer mixture that forms a double layer as claimed in claim
 9. 12. An electronic component which is produced using a polymer mixture as claimed in claim
 2. 13. An electronic component which is produced using a polymer mixture as claimed in claim
 3. 14. An electronic component which is produced using a polymer mixture as claimed in claim
 4. 15. An electronic component which is produced using a polymer mixture as claimed in claim
 5. 16. An electronic component which is produced using a polymer mixture as claimed in claim
 6. 17. An electronic component which is produced using a polymer mixture as claimed in claim
 7. 18. A printing process for the production of a semiconductive double layer by a known process, selected from the group consisting of screen printing, flexographic printing, offset printing, gravure printing and/or pad printing process, the double layer produced by printing a printing medium comprising the polymer mixture of claim 2 for forming the one or more semiconductive polymers in a first of its layers, and the one or more non-semiconductive polymers in a second of its layers.
 19. A printing process for the production of a semiconductive double layer by a known process, selected from the group consisting of screen printing, flexographic printing, offset printing, gravure printing and/or pad printing process, the double layer produced by printing a printing medium comprising the polymer mixture of claim 3 for forming the one or more semiconductive polymers in a first of its layers, and the one or more non-semiconductive polymers in a second of its layers.
 20. An electronic component comprising: a substrate; and on the substrate: a polymer mixture, the polymer mixture comprising first and second materials having respective semiconductive and non-semiconductive properties, the mixture comprising: one or more semiconductive polymers, and one or more non-semiconductive polymers, wherein the semiconductive and non-semiconductive polymers separate from one another after deposition on the substrate forming separate and discrete semiconductor and non-semiconductor layers on the substrate. 